US6110566A - Stabilization of fluorescent dyes in vinyl articles using hindered amine light stabilizers - Google Patents

Stabilization of fluorescent dyes in vinyl articles using hindered amine light stabilizers Download PDF

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Publication number
US6110566A
US6110566A US08/956,332 US95633297A US6110566A US 6110566 A US6110566 A US 6110566A US 95633297 A US95633297 A US 95633297A US 6110566 A US6110566 A US 6110566A
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US
United States
Prior art keywords
article
hindered amine
fluorescent
polyvinyl chloride
retroreflective
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Expired - Lifetime
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US08/956,332
Inventor
Kenneth M. White
Lee A. Pavelka
Vera L. Lightle
James C. Coderre
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3M Innovative Properties Co
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3M Innovative Properties Co
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Application filed by 3M Innovative Properties Co filed Critical 3M Innovative Properties Co
Priority to US08/956,332 priority Critical patent/US6110566A/en
Priority to CA 2308253 priority patent/CA2308253C/en
Priority to CNB988108895A priority patent/CN1139628C/en
Priority to JP2000517017A priority patent/JP2001520293A/en
Priority to EP98908695A priority patent/EP1025156B1/en
Priority to PCT/US1998/003577 priority patent/WO1999020688A1/en
Priority to DE1998609280 priority patent/DE69809280T2/en
Priority to AU66660/98A priority patent/AU6666098A/en
Priority to KR10-2000-7004357A priority patent/KR100518493B1/en
Assigned to MINNESOTA MINING AND MANUFACTURING COMPANY reassignment MINNESOTA MINING AND MANUFACTURING COMPANY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: CODERRE, JAMES C., PAVELKA, LEE A., LIGHTLE, VERA L., WHITE, KENNETH M.
Priority to TW87117494A priority patent/TW538123B/en
Assigned to 3M INNOVATIVE PROPERTIES COMPANY reassignment 3M INNOVATIVE PROPERTIES COMPANY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: MINNESOTA MINING AND MANUFACTURING COMPANY, A CORPORATION OF DELAWARE
Priority to US09/593,335 priority patent/US6406798B2/en
Publication of US6110566A publication Critical patent/US6110566A/en
Application granted granted Critical
Priority to US10/028,162 priority patent/US6526588B2/en
Priority to US10/304,501 priority patent/US7449514B2/en
Priority to US11/126,683 priority patent/US20050213213A1/en
Priority to US11/467,031 priority patent/US7468406B2/en
Priority to JP2007258032A priority patent/JP5280663B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B44DECORATIVE ARTS
    • B44FSPECIAL DESIGNS OR PICTURES
    • B44F1/00Designs or pictures characterised by special or unusual light effects
    • B44F1/08Designs or pictures characterised by special or unusual light effects characterised by colour effects
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/06Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/18Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/30Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/30Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/304Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B3/00Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form
    • B32B3/26Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
    • B32B3/30Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by a layer formed with recesses or projections, e.g. hollows, grooves, protuberances, ribs
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B44DECORATIVE ARTS
    • B44FSPECIAL DESIGNS OR PICTURES
    • B44F1/00Designs or pictures characterised by special or unusual light effects
    • B44F1/02Designs or pictures characterised by special or unusual light effects produced by reflected light, e.g. matt surfaces, lustrous surfaces
    • B44F1/04Designs or pictures characterised by special or unusual light effects produced by reflected light, e.g. matt surfaces, lustrous surfaces after passage through surface layers, e.g. pictures with mirrors on the back
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/0008Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00Other synthetic dyes of known constitution
    • C09B57/14Benzoxanthene dyes; Benzothioxanthene dyes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0001Post-treatment of organic pigments or dyes
    • C09B67/002Influencing the physical properties by treatment with an amine
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0097Dye preparations of special physical nature; Tablets, films, extrusion, microcapsules, sheets, pads, bags with dyes
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/12Reflex reflectors
    • G02B5/122Reflex reflectors cube corner, trihedral or triple reflector type
    • G02B5/124Reflex reflectors cube corner, trihedral or triple reflector type plural reflecting elements forming part of a unitary plate or sheet
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/12Reflex reflectors
    • G02B5/126Reflex reflectors including curved refracting surface
    • G02B5/128Reflex reflectors including curved refracting surface transparent spheres being embedded in matrix
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00Layers arrangement
    • B32B2250/022 layers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00Layers arrangement
    • B32B2250/24All layers being polymeric
    • B32B2250/246All polymers belonging to those covered by groups B32B27/32 and B32B27/30
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/40Properties of the layers or laminate having particular optical properties
    • B32B2307/402Coloured
    • B32B2307/4026Coloured within the layer by addition of a colorant, e.g. pigments, dyes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/40Properties of the layers or laminate having particular optical properties
    • B32B2307/416Reflective
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/40Properties of the layers or laminate having particular optical properties
    • B32B2307/42Polarizing, birefringent, filtering
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/40Properties of the layers or laminate having particular optical properties
    • B32B2307/422Luminescent, fluorescent, phosphorescent
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2590/00Signboards, advertising panels, road signs
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/24Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/2419Fold at edge
    • Y10T428/24198Channel-shaped edge component [e.g., binding, etc.]
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
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    • Y10T428/00Stock material or miscellaneous articles
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    • Y10T428/24479Structurally defined web or sheet [e.g., overall dimension, etc.] including variation in thickness
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10T428/25Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y10T428/252Glass or ceramic [i.e., fired or glazed clay, cement, etc.] [porcelain, quartz, etc.]
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/29Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2991Coated
    • Y10T428/2993Silicic or refractory material containing [e.g., tungsten oxide, glass, cement, etc.]
    • Y10T428/2996Glass particles or spheres
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10T442/60Nonwoven fabric [i.e., nonwoven strand or fiber material]
    • Y10T442/674Nonwoven fabric with a preformed polymeric film or sheet
    • Y10T442/676Vinyl polymer or copolymer sheet or film [e.g., polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, etc.]

Definitions

  • the present invention pertains to polyvinyl chloride articles that exhibit durable fluorescent colors through the use of selected hindered amine light stabilizers.
  • fluorescent colorants can take light that they absorb for example, in the non-visible region, (e.g., ultraviolet light) and reemit it in the visible spectrum. This innate property allows fluorescent articles to exhibit an enhanced visual contrast between the colored article and its surrounding environment.
  • Burns et al. in U.S. Pat. No. 5,605,761 teach the use of a hindered amine light stabilizer (HALS) to maintain the durability of articles containing fluorescent dyes in a polycarbonate polymeric matrix.
  • HALS hindered amine light stabilizer
  • the fluorescent dye may be thioxanthene, perylene imide, or thioindigoid dyes
  • the HALS may be compounds from the 2,2,6,6-tetraalkyl piperidine class of compounds. While these articles are extremely useful in maintaining fluorescent color stability, they are not very flexible due to the polycarbonate matrix's inherent rigidity.
  • Polyvinyl chloride (PVC) films are useful in many applications because of their flexibility and commercial availability.
  • UV absorbing stabilizers have been commonly used in polyvinyl chloride articles to light stabilize the polymer matrix. See, e.g., Marice McMurrer, Update: UV Stabilizers, PLASTICS COMPOUNDING 40 (January/February 1985). UV stabilizers, however, are not effective in stabilizing fluorescent dyes in the matrix.
  • PVC films containing fluorescent dyes are widely available today, they tend to have very poor color retention. Factors contributing to color fading include lack of dye solubility in the PVC host matrix, dye migration, and minimal protection offered by the resin against photodegradation.
  • HALS with its amine group in the molecular structure, may not be compatible with PVC.
  • T. Hjertberg and E. M. Sorvik stated in Thermal Degradation of PVC, in DEGRADATION AND STABILISATION OF PVC, E. D. Owen (editor) 21, 69 (1984) that amines "induce dehydrochlorination of PVC at high temperatures" leading to degradation of the PVC matrix.
  • HALS based on secondary or tertiary piperidinyl amines are very basic compounds.
  • 2,2,6,6-tertamethyl piperidine has a pk b of 2.9 as compared to 4.7 for ammonia when measured in water.
  • the present invention provides, for the first time, colored articles exhibiting durable fluorescent properties in a solventless PVC host matrix by incorporating a particular class of HALS to stabilize a class of fluorescent dyes. Contrary to known teachings that HALS may not be compatible with PVC, this invention includes the discovery that new combinations of HALS and fluorescent dyes in a PVC host matrix will exhibit superior stabilization of colored, fluorescent articles. Because the PVC host matrix has good mechanical and thermal properties, the inventive article will be useful in many applications, including, but not limited to, uses in clothing, traffic control signs and devices (for example, roll-up signs), backpacks, and water flotation safety devices.
  • the inventive article exhibits durable color and fluorescent properties and comprises (a) a polymeric matrix that contains substantially solventless polyvinyl chloride resin; (b) a thioxanthene fluorescent dye; and (c) a hindered amine light stabilizer comprising at least one secondary or tertiary amine groups and having a molecular weight of less than about 1000 grams/mole.
  • the inventive articles can be made by combining these components into a mixture and forming an article from the mixture.
  • the present invention has the advantage in that it exhibits durable color properties and fluorescence without the need to use protective overlays. If desired, however, a protective overlay may be used to further increase the durability of the inventive article.
  • the inventive articles retain their color and are able to fluoresce for a longer time period than is normally expected even when they are exposed to direct sunlight. Articles of the invention therefore are good candidates for use with retroreflective elements.
  • Another advantage of the invention is that the polymers, dyes, and HALS may be processed in a solventless system, which not only essentially eliminates solvent emissions into the atmosphere but also reduces the article's manufacturing cost by totally eliminating solvent use.
  • FIG. 1 is a cross-sectional view of a retroreflective article 10 in accordance with the invention.
  • FIG. 2 is a cross-sectional view of another embodiment of retroreflective article 20 in accordance with the invention.
  • FIG. 3 is a cross-sectional view of another embodiment of retroreflective article 30 in accordance with the invention.
  • FIG. 4 is a cross-sectional view of another embodiment of retroreflective article 50 in accordance with the invention.
  • FIG. 5 is a cross-sectional view of another embodiment of retroreflective article 70 in accordance with the invention.
  • colorant means pigments or dyes or other substances used to impart hue and chroma to an article
  • conventional colorant means colorants that do not significantly fluoresce when exposed to visible light and/or ultraviolet light and do not exhibit fluorescent properties to the unaided eye;
  • cube film means a single retroreflective film having cube corner elements projecting from one surface thereof;
  • cube corner sheeting means a multilayer retroreflective sheeting that contains cube corner elements
  • durable refers to an enhanced retention of color or fluorescence upon exposure to weathering
  • embedded lens retroreflective base sheet comprises (a) a monolayer of microspheres having a space layer and (b) a reflective layer in optical association with the rear surface of the microspheres and a binder layer in which the front surfaces of the microspheres are embedded;
  • encapsulated lens retroreflective base sheet comprises (a) a monolayer of microspheres having a reflective layer in association with the rear surface of the microspheres and (b) a cover layer disposed over the front surface of the microspheres forming cells;
  • Exposed lens retroreflective base sheet comprises a monolayer of microspheres having a reflective layer in association with the rear surface of microspheres that are embedded in a binder layer;
  • hindered amine light stabilizer means an additive used to light stabilize fluorescent dyes, the stabilizer having at least one secondary or tertiary amine group;
  • polymeric matrix means the principal polymeric material in which the fluorescent dye and hindered amine light stabilizer reside
  • second amine group means a group that contains nitrogen (N) and has one hydrogen (H) atom bonded to the nitrogen atom;
  • tertiary amine group means a group that contains nitrogen (N) and does not have a hydrogen (H) atom bonded to the nitrogen atom;
  • substantially solventless polyvinyl chloride resin means a polymeric polyvinyl chloride resin capable of being processed, whether through extrusion or calendering, without the use of a solvent;
  • thioxanthene fluorescent dye means a fluorescent dye having a thioxanthene unit as part of its molecular structure
  • weathering means exposing an article to either natural or artificial environments including, for example, heat, light, moisture, and ultraviolet radiation.
  • the present invention combines a substantially solventless polyvinyl chloride host matrix with fluorescent dyes, and hindered amine light stabilizers to yield durable, colored fluorescent articles.
  • FIG. 1 shows a cube corner based retroreflective article 10 of the invention.
  • Article 10 (commonly referred to as "cube film”) comprises a multitude of cube corner elements 12 and a land layer 14. Not shown in the figure are fluorescent dyes and hindered amine light stabilizers.
  • Light enters the cube film 10 through the front or first major surface 15. The light then passes through the land layer 14 and strikes the planar faces 11 of the cube corner elements 12 and returns in the direction from which it came as shown by arrow 18.
  • FIG. 2 shows a cube corner based retroreflective article 20 of the invention.
  • Article 20 comprises a body layer 26 disposed on a front or first major surface 25 of a cube film 21.
  • the cube film 21 comprises a multitude of cube corner elements 22 and can optionally include a land layer 24.
  • the body layer 26 comprises a substantially solventless polyvinyl chloride matrix, fluorescent dyes, and hindered amine light stabilizers (all not shown) and is the outermost layer of article 20.
  • the land layer 24 is distinguished from the body layer 26 by being a layer disposed immediately adjacent to the base of the cube corner elements. If desired, the land layer 24, if present, and/or the cube corner elements 22 can comprise a substantially solventless polyvinyl chloride matrix, fluorescent dyes and hindered amine light stabilizers.
  • FIG. 3 shows a microsphere based retroreflective article 30 of the invention.
  • Article 30 comprises a body layer 36 disposed on the front or first major surface 35 of an embedded lens retroreflective base sheet 31.
  • Base sheet 31 comprises a monolayer of microspheres 32 embedded in a binder layer 33 with space layer 34, specular reflective layer 38 and optional adhesive layer 40.
  • the retroreflective base sheet can also be exposed lens or encapsulated lens--see U.S. Pat. Nos. 5,316,838 (Crandall) and 4,025,159 (McGrath) respectively for examples of such sheeting.
  • the body layer 36 comprises a substantially solventless polyvinyl chloride matrix, fluorescent dyes, and hindered amine light stabilizers.
  • articles of the invention may optionally include a protective overlay that may or may not include ultraviolet absorbing agents.
  • the overlay is preferably substantially transparent to visible light and includes a means to screen substantial portions of incident ultraviolet radiation.
  • FIG. 4 illustrates a retroreflective embodiment 50 having a cube film 51.
  • Body layer 56 is disposed on the front or first major surface 55 of cube film 51.
  • an overlay 58 Disposed on a first side 57 of body layer 56 is an overlay 58.
  • body layer 56 comprises a substantially solventless polyvinyl chloride matrix, fluorescent dyes, and hindered amine light stabilizers.
  • Overlay 58 is preferably coextensive with body layer 56 so as to provide the most protection.
  • the polymeric matrix used in the present invention contains substantially solventless polyvinyl chloride as the host matrix.
  • the polymeric matrix does not need to possess other polymers (e.g., acrylic polymers) to impart good durability and thus may consist essentially of solventless polyvinyl chloride.
  • Plasticizers may be incorporated into the matrix to impart desirable physical properties, such as flexibility.
  • Illustrative examples of useful plasticizers include di-2-ethylhexyl phthalate, commercially available as DOP from Aristech Chemical Corp., and diisononyl phthalate, commercially available as JAYFLEX DINP, from Exxon Corp.
  • UV absorbers such as hydroxybenzophenones can be added to stabilize the PVC from ultraviolet light degradation.
  • Other additives that may be added as processing aids include fillers, heat stabilizers, and lubricants.
  • Plasticized PVC is advantageous in that it has excellent flexibility so as to be conformable to a variety of diverse substrates ranging from fabrics to substrates with compound curves, such as a traffic barrel.
  • Articles of the invention have sufficient flexibility to be wound at room temperature about a mandrel, having a diameter of 3 millimeter without cracking.
  • Plasticized PVC can also be attached easily to a substrate, through adhesive means or mechanical means.
  • An illustrative mechanical means involves sewing the inventive product onto a fabric substrate.
  • the substantially solventless PVC films may be made by extruding or calendering PVC resins combined with fluorescent dyes and HALS into a film or cube film having a nominal thickness of about 0.025 millimeters (mm) (0.001 inch) to about 3.2 mm (0.125 inch), preferably about 0.076 mm (0.003 inch) to about 0.5 mm (0.02 inch). The latter range is preferable in that it is more useful for retroreflective sheetings. Film thickness may vary with the particular application. For example, if the application requires high durability, typically a thicker film, on the order of about 0.75 mm (0.030 inch) may be more useful.
  • the thickness of the PVC film or cube film has an affect on the quantity of fluorescent dyes and hindered amine light stabilizers that can be loaded into the film.
  • the fluorescent dyes useful for this invention are dyes from the thioxanthene classes of compounds. A single dye or a combination of dyes may be used.
  • Illustrative commercially available thioxanthene fluorescent dyes useful in the present invention include HOSTASOL® RED GG, HOSTASOL® YELLOW 3G, DAY-GLO® D-304, and DAY-GLO® D-315.
  • a useful fluorescent orange dye is 14H-anthra[2,1,9-mna]thioxanthene-14-one, commercially available as C.I. Solvent Orange 63 (HOSTASOL® RED GG) from Hoescht Celanese, and having the following chemical structure: ##STR1##
  • a useful yellow fluorescent dye is N-octadecyl-benzo[k,1]thioxanthene-3,4-dicarboximide, commercially available as C.I. Solvent Yellow 98 (HOSTASOL® YELLOW 3G) from Hoescht Celanese, and having the following chemical structure: ##STR2##
  • DAY-GLO® D-304 is a thioxanthene compound, available from Day-Glo Color Corp., Cleveland, Ohio.
  • Another useful orange fluorescent dye is DAY-GLO® D-315, also a thioxanthene compound available from Day-Glo Color Corp.
  • the inventive film typically, up to 2 weight percent and preferably about 0.01 weight percent to about 1.0 weight percent of the dye is present in the inventive film.
  • the weight percent is based on the total weight of the inventive film.
  • Dye loadings outside this range may be used in accordance with the invention to achieve the desired color. For example, if the dye is added to a thicker film, a lower dye loading can give the same visual effect. Articles having higher dye loadings generally exhibit brighter fluorescence and deeper color than articles with lower dye loadings of the same dye. Articles having a high dye loading, however, may exhibit a self-quenching phenomenon that occurs when molecules of the dye absorb the energy emitted by neighboring dye molecules. This self-quenching can cause an undesirable decrease in fluorescent brightness.
  • dyes and pigments may be added to the present invention to adjust the color and appearance of the article. Care should be taken, however, to select dyes and pigments, as well as their loadings, so as not to significantly interfere with the performance of the fluorescent dyes in the article. If retroreflective elements are included in the inventive article, the dyes or pigments should not undesirably impair the article's transparency. If the inventive article has reduced transparency, its retroreflective performance may also be undesirably reduced.
  • HALS hindered amine light stabilizer
  • the combination of selected HALS, the substantially solventless polyvinyl chloride host matrix, and selected fluorescent dyes in the present invention prevents an as yet undefined degradation and/or reaction between the dye and the polyvinyl chloride which could otherwise occur.
  • the advantages of the present invention are attained through the combination of the substantially solventless polyvinyl chloride matrix, the thioxanthene fluorescent dye, and the hindered amine light stabilizers described herein.
  • the inventive article typically, up to about 2 weight percent, and preferably about 0.05 to about 1.0 weight percent of the HALS is contained in the inventive article.
  • the weight percent of HALS used is based on the total weight of the inventive film.
  • Illustrative commercially available HALS useful in the present invention include TINUVIN® 770, TINUVIN® 144, and SANDUVO® PR-31.
  • a HALS having the chemical formula of Bis-(2,2,6,6-tetramethyl-4-piperidinyl) sebacate and a molecular weight of about 480 grams/mole, contains secondary amines, is commercially available as TINUVIN®-770 from Ciba-Geigy Corp., and has the following chemical structure: ##STR3##
  • This HALS possesses two secondary amine groups, where the nitrogen atom is bonded to two carbon atoms and a hydrogen atom.
  • a HALS having the chemical formula of Bis-(1,2,2,6,6-pentamethyl-4-piperidinyl)-2-n-butyl-2-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate and a molecular weight of about 685 grams/mole, contains tertiary amines, is commercially available as TINUVIN® 144 from Ciba-Geigy Corp., and has the following chemical structure: ##STR4##
  • a HALS having a chemical formula of propanedioic acid, [(4-methoxyphenyl)-methylene]-bis-(1,2,2,6,6-pentamethyl-4-piperidinyl)ester, and a molecular weight of about 529 grams/mole, contains tertiary amines, is commercially available as SANDUVOR® PR-31 from Clariant Corp., and has the following chemical structure: ##STR5##
  • TINUVIN® 144 and SANDUVOR® PR-31 each possesses two tertiary amine groups, where the nitrogen atom is bonded to three carbon atoms.
  • the inventive film can be made using an extrusion or a calendering method. Although both methods are useful in producing a substantially flat film, they do so by different processes. Extrusion involves processing a viscous melt under pressure to force it through a shaping die in a continuous stream to form a film. Calendering takes a mass of fused, viscous material and feeds it between successive pairs of co-rotating, parallel rolls to form a film. Extrusion has the advantage in that if a cube film is desired, the feed stock leaving the extruder can be nipped directly into a mold having cube corner recesses. Calendering, on the other hand, has the advantage in that flexible PVC films can be economically produced using this process.
  • a method of making an article exhibiting durable color and fluorescent properties can comprise: (a) combining substantially solventless polyvinyl chloride resin, a thioxanthene fluorescent dye, and a hindered amine light stabilizer comprising at least one secondary or tertiary amine groups having a molecular weight less than 1000 grams/mole into a mixture; and (b) forming the article from the mixture.
  • the polymeric resin/dye/HALS mixture is first tumble mixed together.
  • the polymeric resin is typically in the form of small granules.
  • the mixture is fed into an extruder where, with the presence of heat and rotational action of the screw, the mixture is mixed and changes into a viscous melt.
  • an extruder with multiple zones of heating is used.
  • the extrusion temperature should be chosen to melt the components but not be so high so as to degrade them. Suitable extrusion temperatures, when using the fluorescent dyes and HALS described above, range from about 175° C. to about 205° C.
  • the melt leaving the extrusion dye is allowed to contact a chrome roll or polished casting roll to form a substantially flat film.
  • the melt leaving the extrusion die is allowed to contact a mold or tool having cube corner recesses therein.
  • a cube corner film is formed having, preferably, a minimal land layer and a multitude of cube corner elements whose base plane is adjacent to the land layer. See, for example, U.S. Pat. No. 5,450,235 (Smith et al.) and International Publication No. WO 95/11464 (Benson et al.) for descriptions of methods of producing a cube corner sheeting.
  • Extrusion is the preferred method for making an inventive cube film.
  • the cube corner elements may optionally be vapor coated with a metallic layer, such as vapor deposited aluminum or silver, to increase retroreflective performance. Vapor coating the cube corner elements, however, may cause the fluorescent cube film to have a gray appearance, which may be undesirable for some applications.
  • the polyvinyl chloride resin typically in powder form
  • the fluorescent dye and the hindered amine light stabilizer are added to mixing unit for intensive mixing.
  • Other additives such as plasticizers, UV absorbers, heat stabilizers, fillers, and lubricants may be added for desired physical properties and/or as processing aids.
  • the mixing unit has a ribbon type blade and can be jacketed for heating and cooling.
  • the PVC powder absorbs the additives, including the dye and HALS, to form a powder mix.
  • the powder is typically cooled and fed through a screen to remove metals because the metal particles, if present, can damage the calender roll surface.
  • the screened powder mixture is typically fed into a fluxing unit for continuous mixing causing the mixture to become a fused, viscous mass that is feed stock to be delivered to the calender rolls.
  • the calender rolls typically in a four roll setup, can be heated. In making the inventive article, the calender rolls are heated so that their surface temperature ranges from about 170° C. to about 180° C. (340 to 355° F.). Configuration of the rolls can also be an important factor.
  • the viscous, fused feedstock is fed to the calender where the film or sheet is formed with the film thickness controlled by the gap between the final rolls.
  • Calendering is a preferred method for making the inventive film because of economic efficiencies.
  • Substantially flat films can be laminated to a preexisting retroreflective base sheet, such as cube corner based or microsphere based sheets.
  • the film is laminated to the front or first major surface of retroreflective base sheets to produce a new retroreflective article in accordance with the present invention.
  • the body layer 26 typically a substantially flat film
  • the body layer 36 is laminated to a front or first major surface 35 of microsphere based retroreflective base sheet 31 to produce a retroreflective article 30 of the invention.
  • the inventive films are used as a carrier for radiation cured cube corner elements.
  • These cube corner elements comprise reactive resins capable of being crosslinked by a free radical polymerization mechanism by exposure to actinic radiation, for example, electron beam, ultraviolet light, or visible light. See U.S. Pat. No. 5,450,235 (Smith et al.) and International Publication No. WO 95/11464 for examples of such reactive resins.
  • the reactive resin is preferably cured in situ on the inventive film.
  • FIG. 5 shows a cube corner based retroreflective article 70 of the invention manufactured in accordance with the principles of the invention disclosed in International Publication No. WO 95/11464 published Apr.
  • FIG. 5 is designed to be a highly flexible retroreflective sheeting suitable for conforming to corrugated and/or flexible surfaces.
  • retroreflective article 70 comprises a multitude of substantially independent cube corner elements 72 and a body layer 76 having two major surfaces 71 and 73, the cube corner elements projecting from the first major surface 73 and have zero to minimal land.
  • this embodiment has essentially no land layer and the front surface 75 of the cube corner elements is juxtaposed against surface 73.
  • body layer 76 comprises substantially solventless polyvinyl chloride matrix, fluorescent dyes and hindered amine light stabilizers (all not shown) and is the outermost layer of article 70.
  • the light source was a 6500-watt, water-cooled xenon arc device that has borosilicate inner and outer filters.
  • the light source exhibits an irradiance of about 0.55 watts/meter 2 .
  • the weathering cycle consisted of 102 minutes of light at a Black Panel temperature (as defined in the test method) of about 63° C., followed by 18 minutes of exposure while subjecting the sample to deionized water spray.
  • UV-Vis Ultraviolet-Visible
  • the amount of fluorescent dye retained in a sample was determined by measuring the major dye absorption band (456 nanometers (nm)) using UV-Vis spectroscopy before and after the sample was subjected to weathering.
  • An illustrative UV-Vis spectrophotometer used was a Shimadzu model UV2101-PC.
  • a decrease in absorbance is related to a reduction in dye concentration.
  • a “percent dye retention” value was calculated as the ratio of the peak absorbance in the weathered sample to the peak absorbance of the original unweathered sample.
  • a polyvinyl chloride film having a thickness of about 0.089 mm (0.0035 inch) to about 0.11 mm (0.0045 inch) was made as follows.
  • PVC resin formulation S00354 containing UV absorbers from Alpha Chemical and Plastics Corp.
  • the resin/dye/HALS mixture was tumbled mixed. It was then extruded into a substantially flat film using a single screw extruder with 5 heating zones set at about 175, 205, 205, 175 and 175° C. and the film die set at about 180° C.
  • the extruder was a three-quarters (3/4) inch single screw Brabender extruder with polished chrome rolls.
  • Examples 2 and 3 and Comparative Examples A to E are all made according to Example 1 with different HALS used or no HALS used as described in Table 1. The samples were subjected to 100 hours of accelerated weathering, and the data are reported in Table 1.
  • Examples 4 to 6 were made according to Example 1 except that different fluorescent dyes were used as shown in Table 2. Unless otherwise specified, the samples were subjected to 100 hours of accelerated weathering, and the data are reported in Table 2.
  • Comparative Examples E to N were made according to Example 1 but different fluorescent dyes were used with and without HALS as shown in Table 2. Unless otherwise specified, the samples were subjected to 100 hours of accelerated weathering, and the data are reported in Table 2.
  • a polyvinyl chloride film was made using a pilot scale calendering process as follows.
  • a powder of PVC was mixed with about 0.2% SY98 fluorescent dye and about 0.5% T-770 HALS.
  • Other additives for example UV absorbers, heat stabilizers, plasticizers, lubricants, and fillers were added either for processing aid or to help make a flexible PVC film.
  • the mixture was fed through a strainer to remove metal, if present.
  • the mixture was continuously mixed to form a fused mass, milled, and fed through rolls, all heated at about 177° C. (350° F.), to form the inventive film about 0.13 mm to about 0.15 mm (0.005 to 0.006 inch) thick.
  • the sample was subjected to 400 hours of accelerated weathering and the data are reported in Table 3 below.
  • a calendered PVC film was made according to Example 7 except that no HALS was added to the PVC powder.
  • the sample was subjected to 400 hours of accelerated weathering, and the data are reported in Table 3.
  • calendered PVC film of the invention containing a fluorescent dye and a HALS clearly outperformed a sample that did not contain a HALS.
  • extruded PVC film of the invention containing a fluorescent dye and a HALS outperformed a sample that did not contain a HALS.

Abstract

A durable colored article having fluorescent properties comprises a substantially solventless polyvinyl chloride matrix, a thioxanthene fluorescent dye, and a secondary or tertiary hindered amine light stabilizer having a molecular weight less than about 1000 grams/mole. The invention has the advantage in that it provides a flexible polyvinyl chloride film that exhibits durable fluorescent colors.

Description

TECHNICAL FIELD
The present invention pertains to polyvinyl chloride articles that exhibit durable fluorescent colors through the use of selected hindered amine light stabilizers.
BACKGROUND
Articles containing colorants lose their color when exposed to solar radiation for extended time periods. For example, articles placed outdoors throughout the summer often tend to display a faded version of their original color by the time autumn arrives. Although this fading occurs in both conventional and fluorescent colorants, the problem is more acute with fluorescent colorants.
The life of fluorescent colored articles that are exposed to daily solar radiation is typically in the range of months whereas the life of articles that use conventional colorants can be in the range of years. Although generally less stable, fluorescent colorants nonetheless find frequent use because of their ability to increase an article's visibility. Unlike conventional colorants, fluorescent colorants can take light that they absorb for example, in the non-visible region, (e.g., ultraviolet light) and reemit it in the visible spectrum. This innate property allows fluorescent articles to exhibit an enhanced visual contrast between the colored article and its surrounding environment.
Investigators in the retroreflective art have attempted to stabilize polymeric articles containing fluorescent colorants using various means. For example, Burns et al. in U.S. Pat. No. 5,605,761 teach the use of a hindered amine light stabilizer (HALS) to maintain the durability of articles containing fluorescent dyes in a polycarbonate polymeric matrix. The document further discloses that the fluorescent dye may be thioxanthene, perylene imide, or thioindigoid dyes, and the HALS may be compounds from the 2,2,6,6-tetraalkyl piperidine class of compounds. While these articles are extremely useful in maintaining fluorescent color stability, they are not very flexible due to the polycarbonate matrix's inherent rigidity.
Others, such as Pavelka et al. in U.S. Pat. No. 5,387,458 have attempted to maintain fluorescent colors by using an ultraviolet screening layer that screens out ultraviolet (UV) radiation in the range of 340 to 400 nanometers. The fluorescent color residues in a layer separate from the screening layer. Although these articles are highly beneficial because of fluorescent colors stability, they do present the need of having two separate layers that can add cost to the construction. Furthermore, the screening layer may not be effective in reducing the degradation of the fluorescent dye caused by dye absorbtion of visible radiation.
Polyvinyl chloride (PVC) films are useful in many applications because of their flexibility and commercial availability. UV absorbing stabilizers have been commonly used in polyvinyl chloride articles to light stabilize the polymer matrix. See, e.g., Marice McMurrer, Update: UV Stabilizers, PLASTICS COMPOUNDING 40 (January/February 1985). UV stabilizers, however, are not effective in stabilizing fluorescent dyes in the matrix.
Although PVC films containing fluorescent dyes are widely available today, they tend to have very poor color retention. Factors contributing to color fading include lack of dye solubility in the PVC host matrix, dye migration, and minimal protection offered by the resin against photodegradation.
Technical publications have suggested that HALS, with its amine group in the molecular structure, may not be compatible with PVC. For example, T. Hjertberg and E. M. Sorvik stated in Thermal Degradation of PVC, in DEGRADATION AND STABILISATION OF PVC, E. D. Owen (editor) 21, 69 (1984) that amines "induce dehydrochlorination of PVC at high temperatures" leading to degradation of the PVC matrix. In addition, HALS based on secondary or tertiary piperidinyl amines are very basic compounds. For example, 2,2,6,6-tertamethyl piperidine has a pkb of 2.9 as compared to 4.7 for ammonia when measured in water. See Can Zhang et al., Hindered Amine Light Stabilizers: Effects of Acid Exposure, Volume 24 of JOURNAL OF POLYMER SCIENCE: PART C: POLYMER LETTERS 453, 453 (1986). Because of its alkalinity, HALS in the presence of a volatile acid, such as hydrochloric acid (HCl), forms a salt. Hydrochloric acid is produced by degradation and oxidation reactions resulting from "light induced aging of PVC films." See Martinez et al., Prediction of Photoageing Stability of Plasticized PVC Films Containing UV-Stabilisers, Volume 54 of POLYMER DEGRADATION AND STABILITY 49, 49 (1996). The presence of a basic HALS in combination with a readily available source of HCl gives rise to acid-base reactions that can degrade the PVC matrix.
Because of the flexible nature of PVC films and the desirability using of fluorescent colorants in many articles, there is a need for a durable colored article having these combinations.
SUMMARY OF THE INVENTION
The present invention provides, for the first time, colored articles exhibiting durable fluorescent properties in a solventless PVC host matrix by incorporating a particular class of HALS to stabilize a class of fluorescent dyes. Contrary to known teachings that HALS may not be compatible with PVC, this invention includes the discovery that new combinations of HALS and fluorescent dyes in a PVC host matrix will exhibit superior stabilization of colored, fluorescent articles. Because the PVC host matrix has good mechanical and thermal properties, the inventive article will be useful in many applications, including, but not limited to, uses in clothing, traffic control signs and devices (for example, roll-up signs), backpacks, and water flotation safety devices.
In brief summary, the inventive article exhibits durable color and fluorescent properties and comprises (a) a polymeric matrix that contains substantially solventless polyvinyl chloride resin; (b) a thioxanthene fluorescent dye; and (c) a hindered amine light stabilizer comprising at least one secondary or tertiary amine groups and having a molecular weight of less than about 1000 grams/mole. The inventive articles can be made by combining these components into a mixture and forming an article from the mixture.
Because processing of a substantially solventless polyvinylchloride resin subjects the resin to high temperatures, it was not predicted that a durable fluorescent-colored article would result. As indicated above, amines can induce dehydrochlorination of the polyvinyl chloride at high temperatures, which can lead to degradation of the polyvinyl chloride matrix. Notwithstanding this concept, the inventive article is surprisingly durable. Thus, the combination of using substantially solventless polyvinyl chloride and HALS provides benefits unsuggested in the art for forming durable fluorescent-colored, PVC articles.
The present invention has the advantage in that it exhibits durable color properties and fluorescence without the need to use protective overlays. If desired, however, a protective overlay may be used to further increase the durability of the inventive article. The inventive articles retain their color and are able to fluoresce for a longer time period than is normally expected even when they are exposed to direct sunlight. Articles of the invention therefore are good candidates for use with retroreflective elements.
Another advantage of the invention is that the polymers, dyes, and HALS may be processed in a solventless system, which not only essentially eliminates solvent emissions into the atmosphere but also reduces the article's manufacturing cost by totally eliminating solvent use.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention will be further explained with reference to the drawings, wherein:
FIG. 1 is a cross-sectional view of a retroreflective article 10 in accordance with the invention;
FIG. 2 is a cross-sectional view of another embodiment of retroreflective article 20 in accordance with the invention;
FIG. 3 is a cross-sectional view of another embodiment of retroreflective article 30 in accordance with the invention;
FIG. 4 is a cross-sectional view of another embodiment of retroreflective article 50 in accordance with the invention; and
FIG. 5 is a cross-sectional view of another embodiment of retroreflective article 70 in accordance with the invention.
These figures are idealized, are not to scale, and are intended to be merely illustrative and non-limiting.
DEFINITIONS
As used herein:
"colorant" means pigments or dyes or other substances used to impart hue and chroma to an article;
"conventional colorant" means colorants that do not significantly fluoresce when exposed to visible light and/or ultraviolet light and do not exhibit fluorescent properties to the unaided eye;
"cube film" means a single retroreflective film having cube corner elements projecting from one surface thereof;
"cube corner sheeting" means a multilayer retroreflective sheeting that contains cube corner elements;
"durable" refers to an enhanced retention of color or fluorescence upon exposure to weathering;
"embedded lens" retroreflective base sheet comprises (a) a monolayer of microspheres having a space layer and (b) a reflective layer in optical association with the rear surface of the microspheres and a binder layer in which the front surfaces of the microspheres are embedded;
"encapsulated lens" retroreflective base sheet comprises (a) a monolayer of microspheres having a reflective layer in association with the rear surface of the microspheres and (b) a cover layer disposed over the front surface of the microspheres forming cells;
"exposed lens" retroreflective base sheet comprises a monolayer of microspheres having a reflective layer in association with the rear surface of microspheres that are embedded in a binder layer;
"hindered amine light stabilizer" means an additive used to light stabilize fluorescent dyes, the stabilizer having at least one secondary or tertiary amine group;
"polymeric matrix" means the principal polymeric material in which the fluorescent dye and hindered amine light stabilizer reside;
"secondary amine group" means a group that contains nitrogen (N) and has one hydrogen (H) atom bonded to the nitrogen atom;
"tertiary amine group" means a group that contains nitrogen (N) and does not have a hydrogen (H) atom bonded to the nitrogen atom;
"substantially solventless polyvinyl chloride resin" means a polymeric polyvinyl chloride resin capable of being processed, whether through extrusion or calendering, without the use of a solvent;
"thioxanthene fluorescent dye" means a fluorescent dye having a thioxanthene unit as part of its molecular structure;
"weathering" means exposing an article to either natural or artificial environments including, for example, heat, light, moisture, and ultraviolet radiation.
DETAILED DESCRIPTION OF THE ILLUSTRATED EMBODIMENTS
The present invention combines a substantially solventless polyvinyl chloride host matrix with fluorescent dyes, and hindered amine light stabilizers to yield durable, colored fluorescent articles.
FIG. 1 shows a cube corner based retroreflective article 10 of the invention. Article 10 (commonly referred to as "cube film") comprises a multitude of cube corner elements 12 and a land layer 14. Not shown in the figure are fluorescent dyes and hindered amine light stabilizers. Light enters the cube film 10 through the front or first major surface 15. The light then passes through the land layer 14 and strikes the planar faces 11 of the cube corner elements 12 and returns in the direction from which it came as shown by arrow 18.
FIG. 2 shows a cube corner based retroreflective article 20 of the invention. Article 20 comprises a body layer 26 disposed on a front or first major surface 25 of a cube film 21. The cube film 21 comprises a multitude of cube corner elements 22 and can optionally include a land layer 24. In a preferred embodiment, the body layer 26 comprises a substantially solventless polyvinyl chloride matrix, fluorescent dyes, and hindered amine light stabilizers (all not shown) and is the outermost layer of article 20. The land layer 24 is distinguished from the body layer 26 by being a layer disposed immediately adjacent to the base of the cube corner elements. If desired, the land layer 24, if present, and/or the cube corner elements 22 can comprise a substantially solventless polyvinyl chloride matrix, fluorescent dyes and hindered amine light stabilizers.
FIG. 3 shows a microsphere based retroreflective article 30 of the invention. Article 30 comprises a body layer 36 disposed on the front or first major surface 35 of an embedded lens retroreflective base sheet 31. For an illustrative example of an embedded lens sheet, see U.S. Pat. No. 4,505,967 (Bailey). Base sheet 31 comprises a monolayer of microspheres 32 embedded in a binder layer 33 with space layer 34, specular reflective layer 38 and optional adhesive layer 40. Light enters retroreflective article 30 through its front surface 41. The light then passes through the body layer 36 and the binder layer 33, strikes microspheres 32, passes through space layer 34 to strike the specular reflective layer 38, and returns in the direction from which it came as shown by arrow 37.
The retroreflective base sheet can also be exposed lens or encapsulated lens--see U.S. Pat. Nos. 5,316,838 (Crandall) and 4,025,159 (McGrath) respectively for examples of such sheeting. In a preferred embodiment, the body layer 36 comprises a substantially solventless polyvinyl chloride matrix, fluorescent dyes, and hindered amine light stabilizers.
Although not necessary, articles of the invention may optionally include a protective overlay that may or may not include ultraviolet absorbing agents. The overlay is preferably substantially transparent to visible light and includes a means to screen substantial portions of incident ultraviolet radiation. FIG. 4 illustrates a retroreflective embodiment 50 having a cube film 51. Body layer 56 is disposed on the front or first major surface 55 of cube film 51. Disposed on a first side 57 of body layer 56 is an overlay 58. In a preferred embodiment, body layer 56 comprises a substantially solventless polyvinyl chloride matrix, fluorescent dyes, and hindered amine light stabilizers. Overlay 58 is preferably coextensive with body layer 56 so as to provide the most protection.
The polymeric matrix used in the present invention contains substantially solventless polyvinyl chloride as the host matrix. The polymeric matrix does not need to possess other polymers (e.g., acrylic polymers) to impart good durability and thus may consist essentially of solventless polyvinyl chloride. Plasticizers may be incorporated into the matrix to impart desirable physical properties, such as flexibility. Illustrative examples of useful plasticizers include di-2-ethylhexyl phthalate, commercially available as DOP from Aristech Chemical Corp., and diisononyl phthalate, commercially available as JAYFLEX DINP, from Exxon Corp. UV absorbers such as hydroxybenzophenones can be added to stabilize the PVC from ultraviolet light degradation. Other additives that may be added as processing aids include fillers, heat stabilizers, and lubricants.
Plasticized PVC is advantageous in that it has excellent flexibility so as to be conformable to a variety of diverse substrates ranging from fabrics to substrates with compound curves, such as a traffic barrel. Articles of the invention have sufficient flexibility to be wound at room temperature about a mandrel, having a diameter of 3 millimeter without cracking. Plasticized PVC can also be attached easily to a substrate, through adhesive means or mechanical means. An illustrative mechanical means involves sewing the inventive product onto a fabric substrate.
The substantially solventless PVC films may be made by extruding or calendering PVC resins combined with fluorescent dyes and HALS into a film or cube film having a nominal thickness of about 0.025 millimeters (mm) (0.001 inch) to about 3.2 mm (0.125 inch), preferably about 0.076 mm (0.003 inch) to about 0.5 mm (0.02 inch). The latter range is preferable in that it is more useful for retroreflective sheetings. Film thickness may vary with the particular application. For example, if the application requires high durability, typically a thicker film, on the order of about 0.75 mm (0.030 inch) may be more useful. The thickness of the PVC film or cube film has an affect on the quantity of fluorescent dyes and hindered amine light stabilizers that can be loaded into the film.
The fluorescent dyes useful for this invention are dyes from the thioxanthene classes of compounds. A single dye or a combination of dyes may be used. Illustrative commercially available thioxanthene fluorescent dyes useful in the present invention include HOSTASOL® RED GG, HOSTASOL® YELLOW 3G, DAY-GLO® D-304, and DAY-GLO® D-315.
A useful fluorescent orange dye is 14H-anthra[2,1,9-mna]thioxanthene-14-one, commercially available as C.I. Solvent Orange 63 (HOSTASOL® RED GG) from Hoescht Celanese, and having the following chemical structure: ##STR1##
A useful yellow fluorescent dye is N-octadecyl-benzo[k,1]thioxanthene-3,4-dicarboximide, commercially available as C.I. Solvent Yellow 98 (HOSTASOL® YELLOW 3G) from Hoescht Celanese, and having the following chemical structure: ##STR2##
Another useful yellow fluorescent dye is DAY-GLO® D-304, which is a thioxanthene compound, available from Day-Glo Color Corp., Cleveland, Ohio. Another useful orange fluorescent dye is DAY-GLO® D-315, also a thioxanthene compound available from Day-Glo Color Corp.
Typically, up to 2 weight percent and preferably about 0.01 weight percent to about 1.0 weight percent of the dye is present in the inventive film. The weight percent is based on the total weight of the inventive film. Dye loadings outside this range may be used in accordance with the invention to achieve the desired color. For example, if the dye is added to a thicker film, a lower dye loading can give the same visual effect. Articles having higher dye loadings generally exhibit brighter fluorescence and deeper color than articles with lower dye loadings of the same dye. Articles having a high dye loading, however, may exhibit a self-quenching phenomenon that occurs when molecules of the dye absorb the energy emitted by neighboring dye molecules. This self-quenching can cause an undesirable decrease in fluorescent brightness.
Articles that possess excess dye can become opaque--perhaps because some of the excess dye may have not dissolved into the polymeric matrix. For applications that require the inventive articles to be light transmissive, such as applications requiring retroreflection, persons skilled in the art should take care to select an appropriate dye loading so that substantially all of the dye dissolves into the polymeric matrix. For applications that do not require light transmissivity, such as decorative applications, the dye loading may not be as important because opacity is not a problem.
Other dyes and pigments (whether fluorescent or non-fluorescent) may be added to the present invention to adjust the color and appearance of the article. Care should be taken, however, to select dyes and pigments, as well as their loadings, so as not to significantly interfere with the performance of the fluorescent dyes in the article. If retroreflective elements are included in the inventive article, the dyes or pigments should not undesirably impair the article's transparency. If the inventive article has reduced transparency, its retroreflective performance may also be undesirably reduced.
As discussed, numerous technical articles have indicated that a hindered amine light stabilizer (HALS), with its amine group, is not compatible with polyvinyl chlorides. Thus the use of certain HALS to light stabilize the inventive fluorescent colored PVC articles is very surprising.
Without intending to be bound by theory, it is believed that the combination of selected HALS, the substantially solventless polyvinyl chloride host matrix, and selected fluorescent dyes in the present invention prevents an as yet undefined degradation and/or reaction between the dye and the polyvinyl chloride which could otherwise occur. Insofar as we know, the advantages of the present invention are attained through the combination of the substantially solventless polyvinyl chloride matrix, the thioxanthene fluorescent dye, and the hindered amine light stabilizers described herein.
Typically, up to about 2 weight percent, and preferably about 0.05 to about 1.0 weight percent of the HALS is contained in the inventive article. The weight percent of HALS used is based on the total weight of the inventive film.
Illustrative commercially available HALS useful in the present invention include TINUVIN® 770, TINUVIN® 144, and SANDUVO® PR-31.
A HALS, having the chemical formula of Bis-(2,2,6,6-tetramethyl-4-piperidinyl) sebacate and a molecular weight of about 480 grams/mole, contains secondary amines, is commercially available as TINUVIN®-770 from Ciba-Geigy Corp., and has the following chemical structure: ##STR3##
This HALS possesses two secondary amine groups, where the nitrogen atom is bonded to two carbon atoms and a hydrogen atom.
A HALS, having the chemical formula of Bis-(1,2,2,6,6-pentamethyl-4-piperidinyl)-2-n-butyl-2-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate and a molecular weight of about 685 grams/mole, contains tertiary amines, is commercially available as TINUVIN® 144 from Ciba-Geigy Corp., and has the following chemical structure: ##STR4##
A HALS, having a chemical formula of propanedioic acid, [(4-methoxyphenyl)-methylene]-bis-(1,2,2,6,6-pentamethyl-4-piperidinyl)ester, and a molecular weight of about 529 grams/mole, contains tertiary amines, is commercially available as SANDUVOR® PR-31 from Clariant Corp., and has the following chemical structure: ##STR5##
TINUVIN® 144 and SANDUVOR® PR-31 each possesses two tertiary amine groups, where the nitrogen atom is bonded to three carbon atoms.
Method of Making
The inventive film can be made using an extrusion or a calendering method. Although both methods are useful in producing a substantially flat film, they do so by different processes. Extrusion involves processing a viscous melt under pressure to force it through a shaping die in a continuous stream to form a film. Calendering takes a mass of fused, viscous material and feeds it between successive pairs of co-rotating, parallel rolls to form a film. Extrusion has the advantage in that if a cube film is desired, the feed stock leaving the extruder can be nipped directly into a mold having cube corner recesses. Calendering, on the other hand, has the advantage in that flexible PVC films can be economically produced using this process.
A method of making an article exhibiting durable color and fluorescent properties can comprise: (a) combining substantially solventless polyvinyl chloride resin, a thioxanthene fluorescent dye, and a hindered amine light stabilizer comprising at least one secondary or tertiary amine groups having a molecular weight less than 1000 grams/mole into a mixture; and (b) forming the article from the mixture.
Typically, in an extrusion process the polymeric resin/dye/HALS mixture is first tumble mixed together. The polymeric resin is typically in the form of small granules. The mixture is fed into an extruder where, with the presence of heat and rotational action of the screw, the mixture is mixed and changes into a viscous melt. Typically, an extruder with multiple zones of heating is used. The extrusion temperature should be chosen to melt the components but not be so high so as to degrade them. Suitable extrusion temperatures, when using the fluorescent dyes and HALS described above, range from about 175° C. to about 205° C. Typically, the melt leaving the extrusion dye is allowed to contact a chrome roll or polished casting roll to form a substantially flat film.
If desired, the melt leaving the extrusion die is allowed to contact a mold or tool having cube corner recesses therein. When the melt is nipped into the mold, a cube corner film is formed having, preferably, a minimal land layer and a multitude of cube corner elements whose base plane is adjacent to the land layer. See, for example, U.S. Pat. No. 5,450,235 (Smith et al.) and International Publication No. WO 95/11464 (Benson et al.) for descriptions of methods of producing a cube corner sheeting. Extrusion is the preferred method for making an inventive cube film.
The cube corner elements may optionally be vapor coated with a metallic layer, such as vapor deposited aluminum or silver, to increase retroreflective performance. Vapor coating the cube corner elements, however, may cause the fluorescent cube film to have a gray appearance, which may be undesirable for some applications.
In a calendering process, the polyvinyl chloride resin (typically in powder form), the fluorescent dye, and the hindered amine light stabilizer are added to mixing unit for intensive mixing. Other additives, such as plasticizers, UV absorbers, heat stabilizers, fillers, and lubricants may be added for desired physical properties and/or as processing aids. Typically the mixing unit has a ribbon type blade and can be jacketed for heating and cooling. During mixing, the PVC powder absorbs the additives, including the dye and HALS, to form a powder mix. After intensive mixing, the powder is typically cooled and fed through a screen to remove metals because the metal particles, if present, can damage the calender roll surface. The screened powder mixture is typically fed into a fluxing unit for continuous mixing causing the mixture to become a fused, viscous mass that is feed stock to be delivered to the calender rolls. The calender rolls, typically in a four roll setup, can be heated. In making the inventive article, the calender rolls are heated so that their surface temperature ranges from about 170° C. to about 180° C. (340 to 355° F.). Configuration of the rolls can also be an important factor. The viscous, fused feedstock is fed to the calender where the film or sheet is formed with the film thickness controlled by the gap between the final rolls.
Although this sequence is typical for a calendering process, many variations are possible depending on the end product desired. Calendering is a preferred method for making the inventive film because of economic efficiencies.
Given what is known in the art about amines inducing dehydrochlorination of PVC at high temperatures, the invention nonetheless discovered that PVC articles produced from calendering or extrusion with temperatures as high as 205° (355° F.) are durable, as shown herein by the examples.
Substantially flat films, whether produced by extrusion or calendering, can be laminated to a preexisting retroreflective base sheet, such as cube corner based or microsphere based sheets. Typically, the film is laminated to the front or first major surface of retroreflective base sheets to produce a new retroreflective article in accordance with the present invention. For example, as shown in FIG. 2, the body layer 26, typically a substantially flat film, is laminated to a front or first major surface 25 of cube film 21 to produce a retroreflective article 20 of the invention. Similarly, in FIG. 3, the body layer 36, typically a substantially flat film, is laminated to a front or first major surface 35 of microsphere based retroreflective base sheet 31 to produce a retroreflective article 30 of the invention.
In a preferred embodiment, the inventive films are used as a carrier for radiation cured cube corner elements. These cube corner elements comprise reactive resins capable of being crosslinked by a free radical polymerization mechanism by exposure to actinic radiation, for example, electron beam, ultraviolet light, or visible light. See U.S. Pat. No. 5,450,235 (Smith et al.) and International Publication No. WO 95/11464 for examples of such reactive resins. The reactive resin is preferably cured in situ on the inventive film. FIG. 5 shows a cube corner based retroreflective article 70 of the invention manufactured in accordance with the principles of the invention disclosed in International Publication No. WO 95/11464 published Apr. 27, 1995, entitled "Ultra-Flexible Retroreflective Cube Corner Composite Sheetings and Methods of Manufacture."The embodiment in FIG. 5 is designed to be a highly flexible retroreflective sheeting suitable for conforming to corrugated and/or flexible surfaces.
As shown in FIG. 5, retroreflective article 70 comprises a multitude of substantially independent cube corner elements 72 and a body layer 76 having two major surfaces 71 and 73, the cube corner elements projecting from the first major surface 73 and have zero to minimal land. Thus, this embodiment has essentially no land layer and the front surface 75 of the cube corner elements is juxtaposed against surface 73. In a preferred embodiment, body layer 76 comprises substantially solventless polyvinyl chloride matrix, fluorescent dyes and hindered amine light stabilizers (all not shown) and is the outermost layer of article 70.
EXAMPLES
The following examples are provided to illustrate different embodiments and details of the invention. Although the examples serve this purpose, the particular ingredients and amounts used as well as other conditions and details are not to be construed in a manner that would unduly limit the scope of this invention. Unless otherwise specified, all percentages are in weight percent.
Accelerated Weathering
To simulate outdoor exposure to sunlight on an accelerated basis, some samples were exposed to accelerated weathering in accordance with a cycle defined by ASTM G-26 Type B, Method A. The light source was a 6500-watt, water-cooled xenon arc device that has borosilicate inner and outer filters. The light source exhibits an irradiance of about 0.55 watts/meter2. The weathering cycle consisted of 102 minutes of light at a Black Panel temperature (as defined in the test method) of about 63° C., followed by 18 minutes of exposure while subjecting the sample to deionized water spray.
Ultraviolet-Visible (UV-Vis) Absorption Spectroscopy
The amount of fluorescent dye retained in a sample was determined by measuring the major dye absorption band (456 nanometers (nm)) using UV-Vis spectroscopy before and after the sample was subjected to weathering. An illustrative UV-Vis spectrophotometer used was a Shimadzu model UV2101-PC.
Following Beer's Law, a decrease in absorbance is related to a reduction in dye concentration. A "percent dye retention" value was calculated as the ratio of the peak absorbance in the weathered sample to the peak absorbance of the original unweathered sample.
The following abbreviations are used in the examples:
______________________________________                                    
Abbreviations                                                             
         Meaning                                                          
______________________________________                                    
PVC      Polyvinyl chloride host matrix                                   
T-770    Hindered amine light stabilizer TINUVIN ® 770                
         Bis-(2,2,6,6-tetramethyl-4-piperidinyl) sebacate                 
         Molecular weight of about 480 grams/mole                         
         Available from Ciba-Geigy Corp., Hawthorne, NY.                  
T-144    Hindered amine light stabilizer TINUVIN ® 144                
         Bis-(1,2,2,6,6-pentamethyl-4-piperidinyl)-2-n-butyl-2-           
         (3,5-di-tert-butyl-4-hydroxybenzyl)malonate                      
         Molecular weight of about 685 grams/mole                         
         Available from Ciba-Geigy Corp.                                  
PR-31    Hindered amine light stabilizer                                  
         Propanedioic acid, [(4-methoxyphenyl)-methylene]-bis-            
         (1,2,2,6,6-pentamethyl-4-piperidinyl)ester                       
         Molecular weight of about 529 grams/mole                         
         Available from Clariant Corp., Charlotte, NC.                    
T-622    Hindered amine light stabilizer TINUVIN ® 622                
         Dimethyl succinate polymer with 4-hydroxy-2,2,6,6-               
         tetramethyl-1-piperidine ethanol                                 
         Molecular weight (M.sub.n) approximately greater than            
         2,500 grams/mole                                                 
         Available from Ciba-Geigy Corp.                                  
C-944    Hindered amine light stabilizer CHIMASORB ® 944 FL           
         Poly [6-[(1,1,3,3-tetramethylbutyl)amino]-s-triazine-2,4-        
         diyl][2,2,6,6-tetramethyl-4-piperidyl)imino]-                    
         hexamethylene[(2,2,6,6-tetramethyl-4-piperidyl)imino)]           
         Molecular weight (M.sub.n) approximately greater than            
         2,500 grams/mole                                                 
         Available from Ciba-Geigy Corp.                                  
T-440    Hindered amine light stabilizer TINUVIN ® 440                
         Low molecular weight acetylated hindered amine                   
         Molecular weight of about 435 grams/mole                         
         Available from Ciba-Geigy Corp.                                  
C-3346   Hindered amine light stabilizer CYASORB ® 3346               
         Oligomeric hindered amine                                        
         Molecular weight (M.sub.n) approximately greater than            
         1,600 grams/mole                                                 
         Available from American Cyanamid Corp.                           
SO63     Thioxanthene orange fluorescent dye HOSTASOL ®               
         RED GG; 14H-anthra[2,1,9-mna]thioxanthene-14-one;                
         Available from Hoechst Celanese, Charlotte, NC.                  
SY98     Thioxanthene yellow fluorescent dye HOSTASOL ®               
         YELLOW 3G N-Octadecyl-benzo[k,1]thioxanthene-                    
         3,4-dicarboximide                                                
         Available from Hoechst Celanese.                                 
D-304    Thioxanthene yellow fluorescent dye DAY-GLO ® 304            
         Available from Day-Glo Color Corp., Cleveland, OH.               
D-315    Thioxanthene orange fluorescent dye DAY-GLO ® 315            
         Available from Day-Glo Color Corp.                               
D-838    Coumarin fluorescent POTOMAC YELLOW ™                         
         D-838 dye                                                        
         Available from Day-Glo Color Corp.                               
RED FB   Anthrapyridone fluorescent red dye FLUORESCENT                   
         RED FB ™                                                      
         Available from Keystone Aniline Corp., Chicago, IL.              
RED 5B   Thioindigoid fluorescent red dye HOSTASOL ®                  
         RED 5B C. I. (color index) Vat Red 41                            
         Available from Hoechst Celanese.                                 
______________________________________                                    
Example 1
A polyvinyl chloride film having a thickness of about 0.089 mm (0.0035 inch) to about 0.11 mm (0.0045 inch) was made as follows. PVC resin (formulation S00354 containing UV absorbers from Alpha Chemical and Plastics Corp.) was mixed with about 0.2% SO63 fluorescent dye and about 0.5% of the T-770 HALS. The resin/dye/HALS mixture was tumbled mixed. It was then extruded into a substantially flat film using a single screw extruder with 5 heating zones set at about 175, 205, 205, 175 and 175° C. and the film die set at about 180° C. The extruder was a three-quarters (3/4) inch single screw Brabender extruder with polished chrome rolls.
The sample was subjected to 100 hours of weathering, and the data are reported in Tables 1 and 2.
Examples 2 and 3, and Comparative Examples A to E are all made according to Example 1 with different HALS used or no HALS used as described in Table 1. The samples were subjected to 100 hours of accelerated weathering, and the data are reported in Table 1.
              TABLE 1                                                     
______________________________________                                    
EXTRUDED PVC FILMS CONTAINING                                             
SO63 FLUORESCENT DYE WITH VARIOUS HALS                                    
                        Percent Dye                                       
                        Retention                                         
                        After 100 hours                                   
Example No.     HALS    weathering                                        
______________________________________                                    
1               T-770   55                                                
2               T-144   66                                                
3               PR-31   61                                                
Comparative A   T-622    9                                                
Comparative B   C-944   14                                                
Comparative C   T-440   11                                                
Comparative D   C-3346  15                                                
Comparative E   None     7                                                
______________________________________                                    
As can be seen from the results of TABLE 1, a sample without any HALS (Comparative E) performed worst in that nearly all of the dye was depleted from the film. HALS that had a molecular weight exceeding 1000 grams/mole (Comparative A, B and D) did poorly in the stabilization of the fluorescent dye. Comparative C, having a molecular weight of 435 grams/mole, did not perform well because it did not contain at least one secondary or tertiary amine group.
Examples 4 to 6 were made according to Example 1 except that different fluorescent dyes were used as shown in Table 2. Unless otherwise specified, the samples were subjected to 100 hours of accelerated weathering, and the data are reported in Table 2.
Comparative Examples E to N were made according to Example 1 but different fluorescent dyes were used with and without HALS as shown in Table 2. Unless otherwise specified, the samples were subjected to 100 hours of accelerated weathering, and the data are reported in Table 2.
              TABLE 2                                                     
______________________________________                                    
EXTRUDED PVC FILMS CONTAINING                                             
VARIOUS FLUORESCENT DYES WITH AND WITHOUT HALS                            
                                   Percent Dye                            
Example No.                                                               
           Fluorescent Dye                                                
                        HALS Used  Retention                              
______________________________________                                    
1          SO63         T-770      55                                     
4.sup.a    SY98         T-770      56                                     
5          D-304        T-770      53                                     
6.sup.a    D-315        T-770      39                                     
Comparative E                                                             
           SO63         None       7                                      
Comparative F.sup.a                                                       
           SY98         None       37                                     
Comparative G                                                             
           D-304        None       35                                     
Comparative H.sup.a                                                       
           D-315        None       17                                     
Comparative I                                                             
           D-838        T-770      9                                      
Comparative J                                                             
           RED FB       T-770      13                                     
Comparative K.sup.b                                                       
           RED 5B       T-770      5                                      
Comparative L                                                             
           D-838        None       18                                     
Comparative M                                                             
           RED FB       None       25                                     
Comparative N.sup.b                                                       
           RED 5B       None       3                                      
______________________________________                                    
 .sup.a Sample was subjected to 200 hours of accelerated weathering.      
 .sup.b Sample was subjected to 50 hours of accelerated weathering.       
As shown in Table 2, samples of the invention containing thioxanthene fluorescent dyes with T-770 HALS (Examples 1, 4, 5 and 6) outperformed those samples that did not contain thioxanthene fluorescent dyes stabilized with the same T-770 HALS (Comparatives I, J and K). Those samples that did contain thioxanthene fluorescent dyes but no HALS (Comparatives E, F, G and H) did not retain the dye as well as those that did contain HALS (Examples 1, 4, 5 and 6). Finally, comparing Comparatives I, J and K with Comparatives L, M and N shows that non-thioxanthene fluorescent dye samples do not retain their color even if HALS was used. Thus, in this situation, use of HALS, even if it is the preferred HALS, was ineffective.
Example 7
A polyvinyl chloride film was made using a pilot scale calendering process as follows. A powder of PVC was mixed with about 0.2% SY98 fluorescent dye and about 0.5% T-770 HALS. Other additives, for example UV absorbers, heat stabilizers, plasticizers, lubricants, and fillers were added either for processing aid or to help make a flexible PVC film. The mixture was fed through a strainer to remove metal, if present. The mixture was continuously mixed to form a fused mass, milled, and fed through rolls, all heated at about 177° C. (350° F.), to form the inventive film about 0.13 mm to about 0.15 mm (0.005 to 0.006 inch) thick. The sample was subjected to 400 hours of accelerated weathering and the data are reported in Table 3 below.
Comparative O
A calendered PVC film was made according to Example 7 except that no HALS was added to the PVC powder. The sample was subjected to 400 hours of accelerated weathering, and the data are reported in Table 3.
              TABLE 3                                                     
______________________________________                                    
CALENDERED PVC FILMS                                                      
CONTAINING SY98 FLUORESCENT DYE                                           
                                Percent Dye                               
                                Retention                                 
Example No.                                                               
          HALS     Fluorescent Dye                                        
                                (After 400 hours)                         
______________________________________                                    
7         T-770    SY98         76                                        
Comparative O                                                             
          None     SY98         1.3                                       
______________________________________                                    
As shown in Table 3, calendered PVC film of the invention containing a fluorescent dye and a HALS clearly outperformed a sample that did not contain a HALS.
Example 4 and its comparative counterpart, Comparative E, were both exposed to 400 hours of accelerated weathering, and the data are reported in Table 4.
              TABLE 4                                                     
______________________________________                                    
EXTRUDED PVC FILMS                                                        
CONTAINING SY98 FLUORESCENT DYE                                           
                             Percent Dye Retention                        
Example No.                                                               
         HALS    Fluorescent Dye                                          
                             (After 400 hours)                            
______________________________________                                    
4        T-770   SY98        29                                           
Comparative E                                                             
         None    SY98        9                                            
______________________________________                                    
As shown in Table 4, extruded PVC film of the invention containing a fluorescent dye and a HALS outperformed a sample that did not contain a HALS.
All references cited herein are incorporated by reference in each reference's entirety.

Claims (25)

What is claimed is:
1. An article exhibiting durable color and fluorescent properties comprising:
(a) a polymeric matrix that contains a substantially solventless polyvinyl chloride resin;
(b) a thioxanthene fluorescent dye; and
(c) a hindered amine light stabilizer comprising at least one secondary or tertiary amine groups and having a molecular weight less than about 1000 grams/mole.
2. The article of claim 1, wherein the substantially solventless polyvinyl chloride resin consists essentially of polyvinyl chloride resin.
3. The article of claim 1, wherein the polymeric matrix further comprises plasticized polyvinyl chloride resin.
4. The article of claim 1, wherein the article contains at most about 2 weight percent of the thioxanthene fluorescent dye based on the total weight of the article.
5. The article of claim 1, wherein the article contains about 0.01 to about 1 weight percent of the thioxanthene fluorescent dye based on the total weight of the article.
6. The article of claim 1, wherein the article contains at most about 2 weight percent of the hindered amine light stabilizer based on the total weight of the article.
7. The article of claim 1, wherein the article contains about 0.05 to about 1 weight percent of the hindered amine light stabilizer based on the total weight of the article.
8. The article of claim 1, wherein the hindered amine light stabilizer is selected from at least one of the group consisting of bis-(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis-(1,2,2,6,6-pentamethyl-4-piperidinyl)-2-n-butyl-2-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, and propanedioic acid, [(4-methoxyphenyl)-methylene]-bis-(1,2,2,6,6-pentamethyl-4-piperidinyl)ester.
9. A fluorescent retroreflective article that comprises the article of claim 1.
10. The article of claim 1, wherein the article is a film.
11. The article of claim 1, wherein the article is a retroreflective cube film.
12. The article of claim 1 further comprising a protective overlay.
13. A retroreflective sheeting exhibiting durable color and fluorescent properties comprising:
(a) a retroreflective base sheet having a front surface; and
(b) a body layer disposed on the front surface of the base sheet, the body layer comprising the article of claim 1.
14. The sheeting of claim 13, wherein the retroreflective base sheet is a cube corner based sheeting or a microsphere based sheeting.
15. The sheeting of claim 13, wherein the sheeting is sufficiently flexible to be wound about a mandrel having a diameter of 3 millimeters without cracking.
16. A method of making a retroreflective article, which method comprises placing the article of claim 1 on a retroreflective base sheet.
17. The method of claim 16, wherein the retroreflective base sheet is cube corner based or microsphere based.
18. A method of making an article exhibiting durable color and fluorescent properties comprising:
(a) combining substantially solventless polyvinyl chloride resin, a thioxanthene fluorescent dye, and a hindered amine light stabilizer comprising at least one secondary or tertiary amine groups having a molecular weight less than 1000 grams/mole into a mixture; and
(b) forming the article from the mixture.
19. The method of claim 18, wherein the substantially solventless polyvinyl chloride resin consists essentially of polyvinyl chloride resin.
20. The method of claim 18, wherein the article is formed by either extrusion or calendering.
21. The method of claim 18, wherein the extrusion temperature or calendering temperature is about 175° C. to about 205° C.
22. The method of claim 18, wherein the article contains at most about 2 weight percent of the thioxanthene fluorescent dye based on the total weight of the article.
23. The method of claim 18, wherein the article contains about 0.01 to about 1 weight percent of the thioxanthene fluorescent dye based on the total weight of the article.
24. The method of claim 18, wherein the article contains at most about 2 weight percent of the hindered amine light stabilizer based on the total weight of the article.
25. The method of claim 18, wherein the article contains about 0.05 to about 1 weight percent of the hindered amine light stabilizer based on the total weight of the article.
US08/956,332 1997-10-23 1997-10-23 Stabilization of fluorescent dyes in vinyl articles using hindered amine light stabilizers Expired - Lifetime US6110566A (en)

Priority Applications (16)

Application Number Priority Date Filing Date Title
US08/956,332 US6110566A (en) 1997-10-23 1997-10-23 Stabilization of fluorescent dyes in vinyl articles using hindered amine light stabilizers
KR10-2000-7004357A KR100518493B1 (en) 1997-10-23 1998-02-24 Stabilization of fluorescent dyes in vinyl articles using hindered amine light stabilizers
CNB988108895A CN1139628C (en) 1997-10-23 1998-02-24 Stabilization of fluorescent dyes in vinyl articles using hindered amine light stabilizers
JP2000517017A JP2001520293A (en) 1997-10-23 1998-02-24 Stabilization of fluorescent dyes in vinyl products using hindered amine light stabilizers
CA 2308253 CA2308253C (en) 1997-10-23 1998-02-24 Stabilization of fluorescent dyes in vinyl articles using hindered amine light stabilizers
EP98908695A EP1025156B1 (en) 1997-10-23 1998-02-24 Stabilization of fluorescent dyes in vinyl articles using hindered amine light stabilizers
PCT/US1998/003577 WO1999020688A1 (en) 1997-10-23 1998-02-24 Stabilization of fluorescent dyes in vinyl articles using hindered amine light stabilizers
DE1998609280 DE69809280T2 (en) 1997-10-23 1998-02-24 STABILIZATION OF FLUORESCENT DYES IN VINYL ARTICLES USING STERICALLY HIDDEN AMINE LIGHT STABILIZERS
AU66660/98A AU6666098A (en) 1997-10-23 1998-02-24 Stabilization of fluorescent dyes in vinyl articles using hindered amine light stabilizers
TW87117494A TW538123B (en) 1997-10-23 1999-03-02 Stabilization of fluorescent dyes in vinyl articles using hindered amine light stabilizers
US09/593,335 US6406798B2 (en) 1997-10-23 2000-06-14 Stabilization of fluorescent dyes in vinyl articles using hindered amine light stabilizers
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US11/126,683 US20050213213A1 (en) 1997-10-23 2005-05-11 Stabilization of fluorescent dyes in vinyl articles using hindered amine light stabilizers
US11/467,031 US7468406B2 (en) 1997-10-23 2006-08-24 Stabilization of fluorescent dyes in vinyl articles using hindered amine light stabilizers
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US6323266B2 (en) 1998-01-21 2001-11-27 Reflexite Corporation Extended life fluorescence polyvinyl chloride sheeting
US20020041136A1 (en) * 2000-06-28 2002-04-11 Kenichi Nishikawa Spark plug
US6406798B2 (en) * 1997-10-23 2002-06-18 3M Innovative Properties Company Stabilization of fluorescent dyes in vinyl articles using hindered amine light stabilizers
US6511256B1 (en) 1999-05-27 2003-01-28 Avery Dennison Corporation Pavement marker with improved daytime visibility and fluorescent durability
US6514594B1 (en) 2000-11-09 2003-02-04 Avery Dennison Corporation Fluorescent polymeric articles having screening layer formed from U.V. light absorbing polymer
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US6531205B1 (en) 2001-02-14 2003-03-11 Avery Dennison Corporation Fluorescent yellow retroreflective sheeting
US6533961B2 (en) * 2000-02-22 2003-03-18 3M Innovative Properties Company Durable fluorescent organic pigments and methods of making
US6537679B1 (en) 2000-11-09 2003-03-25 Avery Dennison Corporation Fluorescent articles of glycol-modified polyethylene terephthalate
US20030061671A1 (en) * 2001-08-20 2003-04-03 Shershukov Viktor Mihailovich Thioxanthone dyes with improved solubility and a method of preparing 2-oxybenzanthrones as intermediate materials for making of these dyes
US20030096988A1 (en) * 2001-09-05 2003-05-22 Usha Goswami Multiple fluorescent natural dye compound from a marine organism
US6582730B2 (en) 2001-03-30 2003-06-24 Council Of Scientific & Industrial Research Natural fluorescent dye obtained from a marine invertebrate, compositions containing the said dye and their uses
US20030203211A1 (en) * 2002-04-30 2003-10-30 Guang-Xue Wei Fluorescent articles having multiple film layers
US20030203212A1 (en) * 2002-04-30 2003-10-30 Guang-Xue Wei Fluorescent articles having multiple film layers
US6683124B2 (en) 2001-09-27 2004-01-27 Clariant Finance (Bvi) Limited Fluorescent pigment compositions
US6689391B2 (en) 2001-03-30 2004-02-10 Council Of Scientific & Industrial Research Natural non-polar fluorescent dye from a non-bioluminescent marine invertebrate, compositions containing the said dye and its uses
WO2004073042A2 (en) * 2003-02-12 2004-08-26 Insite Solutions, Llc Article with fabric-backed decorative element and method of fabricating the same
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US6916492B2 (en) 2001-03-30 2005-07-12 Council Of Scientific & Industrial Research Natural nontoxic multicolor fluorescent protein dye from a marine invertebrate, compositions containing the said dye and its uses
US20050154098A1 (en) * 2004-01-09 2005-07-14 Reflexite Corporation Fade-resistant fluorescent retroreflective articles
US6972147B1 (en) 2000-11-09 2005-12-06 Avery Dennison Corporation Fluorescent polymeric articles fabricated from U.V. light absorbing polymer
US20070008790A1 (en) * 2004-05-26 2007-01-11 Buechler Troy R Optical brighteners for display panels
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US20150247297A1 (en) * 2012-11-28 2015-09-03 Evonik Industries Ag New type of road markings for supporting the environment detection of vehicles
US10800970B2 (en) 2015-07-17 2020-10-13 Toray Industries, Inc. Color conversion composition, color conversion film and backlight unit, display and lighting device each comprising same
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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GB9824314D0 (en) * 1998-11-06 1998-12-30 Clariant Int Ltd New hetercyclic compounds
US6472050B1 (en) * 1999-12-30 2002-10-29 Avery Dennison Corporation Light stable fluorescent vinyl suitable for use as a highway retroreflective roll-up sign
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Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3684348A (en) * 1970-09-29 1972-08-15 Rowland Dev Corp Retroreflective material
US4025159A (en) * 1976-02-17 1977-05-24 Minnesota Mining And Manufacturing Company Cellular retroreflective sheeting
US4505967A (en) * 1983-04-11 1985-03-19 Minnesota Mining And Manufacturing Company High-angularity retroreflective sheeting and method for manufacture
US4763985A (en) * 1986-08-01 1988-08-16 Minnesota Mining And Manufacturing Company Retroreflective sheet with enhanced brightness
EP0436464A2 (en) * 1989-12-21 1991-07-10 Ciba-Geigy Ag Photosensitive organic material containing UV-absorbers
US5246991A (en) * 1989-05-23 1993-09-21 Sumitomo Chemical Company, Limited Polyvinyl chloride resin composition
US5316838A (en) * 1991-09-30 1994-05-31 Minnesota Mining And Manufacturing Company Retroreflective sheet with nonwoven elastic backing
EP0612796A1 (en) * 1993-02-23 1994-08-31 Ciba-Geigy Ag Stabilisation of organic pigments
US5387458A (en) * 1990-12-06 1995-02-07 Minnesota Mining And Manufacturing Company Articles exhibiting durable fluorescence with an ultraviolet screening layer
WO1995011464A2 (en) * 1993-10-20 1995-04-27 Minnesota Mining And Manufacturing Company Ultra-flexible retroreflective cube corner composite sheetings and methods of manufacture
US5450235A (en) * 1993-10-20 1995-09-12 Minnesota Mining And Manufacturing Company Flexible cube-corner retroreflective sheeting
WO1996017012A1 (en) * 1994-11-28 1996-06-06 Minnesota Mining And Manufacturing Company Articles exhibiting durable colour and/or fluorescent properties
WO1997008756A1 (en) * 1995-08-28 1997-03-06 Minnesota Mining And Manufacturing Company Durable fluorescent solar collectors
WO1997037252A1 (en) * 1996-04-01 1997-10-09 Reflexite Corporation A color-fast retroreflective structure
US5844024A (en) * 1993-01-18 1998-12-01 Ciba Specialty Chemicals Corporation Cyclic diphenylacetonitriles as stabilizers

Family Cites Families (48)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3830682A (en) 1972-11-06 1974-08-20 Rowland Dev Corp Retroreflecting signs and the like with novel day-night coloration
US4238384A (en) 1978-06-19 1980-12-09 Sandoz, Inc. Method of incorporating additives in polymeric materials
US4336092A (en) * 1980-03-24 1982-06-22 Allan Wasserman Retroreflective fiber and method of making same
US4720356A (en) 1982-03-22 1988-01-19 American Optical Corporation Photochromic composition resistant to fatigue
US4393094A (en) 1982-04-19 1983-07-12 Ford Motor Company Stabilization of electron beam curable compositions for improved exterior durability
US4477608A (en) 1982-08-20 1984-10-16 Ciba-Geigy Corporation Compositions containing graphite
JP2617678B2 (en) 1984-05-10 1997-06-04 三菱化学エムケーブイ 株式会社 Agricultural vinyl chloride resin film
JPS63255594A (en) 1987-04-13 1988-10-21 Ebara Corp Molecular turbopump
JP2844339B2 (en) 1988-07-05 1999-01-06 日本カーバイド工業株式会社 Fluorescent sheet
JP2701371B2 (en) * 1988-08-02 1998-01-21 三菱化学エムケーブイ株式会社 Agricultural vinyl chloride resin fluorescent film
DE58907940D1 (en) 1988-09-09 1994-07-28 Ciba Geigy Ag New compositions containing molybdenum disulfide.
US5004770A (en) 1988-10-19 1991-04-02 Ciba-Geigy Corporation Polymeric substrates stabilized with N-substituted hindered amines
JPH02147651U (en) * 1989-05-09 1990-12-14
DE3933903A1 (en) 1989-10-11 1991-04-18 Basf Ag FLUORESCENT PIGMENTS
US5302497A (en) 1989-12-21 1994-04-12 Ciba-Geigy Corporation Photosensitive organic polymeric material containing UV absorbers
US5989453A (en) 1990-05-11 1999-11-23 Societe Nouvelle De Chimie Industrielle S.A. Process for the manufacture of pigments, especially fluorescent pigments
US5229882A (en) 1990-05-16 1993-07-20 Reflexite Corporation Colored retroreflective sheeting and method of making same
JPH0686715B2 (en) * 1990-10-31 1994-11-02 日東紡績株式会社 Dyeing method for cellulosic cloth
US5135568A (en) 1991-01-30 1992-08-04 Rohm And Haas Company Method for improving fluorescent coatings
US5352753A (en) 1991-04-25 1994-10-04 Allergan, Inc. Ultraviolet light absorbing compounds, silicone compositions and methods for making same
US5415911A (en) 1992-01-16 1995-05-16 Stimsonite Corporation Photoluminescent retroreflective sheeting
EP0597391B1 (en) 1992-11-09 1998-09-09 Central Glass Company, Limited Glass plate with ultraviolet absorbing multilayer coating
DE9216001U1 (en) 1992-11-25 1993-01-14 Roehm Gmbh, 6100 Darmstadt, De
US5405675A (en) 1992-12-10 1995-04-11 Minnesota Mining And Manufacturing Company Embossed multilayer film
US5272562A (en) 1993-02-05 1993-12-21 Minnesota Mining And Manufacturing Company Cube-corner retroreflective articles
EP0776346B1 (en) 1994-08-15 1999-06-02 Witco Vinyl Additives GmbH Stabilised pvdc-containing pvc
US5565151A (en) 1994-09-28 1996-10-15 Reflexite Corporation Retroreflective prism structure with windows formed thereon
JP3390302B2 (en) * 1995-03-17 2003-03-24 住化プラステック株式会社 Antifogging agent composition and agricultural film
ES2186738T3 (en) 1995-03-17 2003-05-16 Sumitomo Chemical Co COMPOSITION OF ANTI-COMPANY COMPANY AND AGRICULTURAL FILM COVERED WITH IT.
JPH0912814A (en) 1995-06-27 1997-01-14 Kyodo Yakuhin Kk Vinyl chloride resin composition
US5672643A (en) 1995-09-29 1997-09-30 Minnesota Mining And Manufacturing Company Fluorescent dye blends
US5920429A (en) 1995-09-29 1999-07-06 Minnesota Mining And Manufacturing Company Fluorescent dye blends
US5674622A (en) 1995-09-29 1997-10-07 Minnesota Mining And Manufacturing Company Fluorescent dye blends
JP3612136B2 (en) * 1996-02-29 2005-01-19 三善加工株式会社 Polyolefin resin composition and laminated film
US6110566A (en) 1997-10-23 2000-08-29 3M Innovative Properties Company Stabilization of fluorescent dyes in vinyl articles using hindered amine light stabilizers
US6001936A (en) 1997-10-24 1999-12-14 3M Innovative Properties Company Dye enhanced durability through controlled dye environment
JP2002507511A (en) 1998-01-21 2002-03-12 リフレキサイト・コーポレーション Long-life polyvinyl chloride fluorescent sheet material
US6511256B1 (en) 1999-05-27 2003-01-28 Avery Dennison Corporation Pavement marker with improved daytime visibility and fluorescent durability
US6472050B1 (en) 1999-12-30 2002-10-29 Avery Dennison Corporation Light stable fluorescent vinyl suitable for use as a highway retroreflective roll-up sign
US6533961B2 (en) 2000-02-22 2003-03-18 3M Innovative Properties Company Durable fluorescent organic pigments and methods of making
US6312132B1 (en) 2000-09-12 2001-11-06 3M Innovative Properties Company Fluorescent red article and retroreflective article made therefrom
US6514594B1 (en) 2000-11-09 2003-02-04 Avery Dennison Corporation Fluorescent polymeric articles having screening layer formed from U.V. light absorbing polymer
US6537679B1 (en) 2000-11-09 2003-03-25 Avery Dennison Corporation Fluorescent articles of glycol-modified polyethylene terephthalate
US20020102389A1 (en) 2000-12-01 2002-08-01 Nielsen Steven M. Retroreflective laminate comprising a tear resistant film
US6531205B1 (en) 2001-02-14 2003-03-11 Avery Dennison Corporation Fluorescent yellow retroreflective sheeting
US6531613B1 (en) 2001-08-20 2003-03-11 3M Innovative Properties Company Thioxanthone dyes with improved solubility
US7264880B2 (en) 2002-04-30 2007-09-04 Avery Dennison Corporation Fluorescent articles having multiple film layers
US20050154098A1 (en) 2004-01-09 2005-07-14 Reflexite Corporation Fade-resistant fluorescent retroreflective articles

Patent Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3684348A (en) * 1970-09-29 1972-08-15 Rowland Dev Corp Retroreflective material
US4025159A (en) * 1976-02-17 1977-05-24 Minnesota Mining And Manufacturing Company Cellular retroreflective sheeting
US4505967A (en) * 1983-04-11 1985-03-19 Minnesota Mining And Manufacturing Company High-angularity retroreflective sheeting and method for manufacture
US4763985A (en) * 1986-08-01 1988-08-16 Minnesota Mining And Manufacturing Company Retroreflective sheet with enhanced brightness
US5246991A (en) * 1989-05-23 1993-09-21 Sumitomo Chemical Company, Limited Polyvinyl chloride resin composition
EP0436464A2 (en) * 1989-12-21 1991-07-10 Ciba-Geigy Ag Photosensitive organic material containing UV-absorbers
US5387458A (en) * 1990-12-06 1995-02-07 Minnesota Mining And Manufacturing Company Articles exhibiting durable fluorescence with an ultraviolet screening layer
US5316838A (en) * 1991-09-30 1994-05-31 Minnesota Mining And Manufacturing Company Retroreflective sheet with nonwoven elastic backing
US5844024A (en) * 1993-01-18 1998-12-01 Ciba Specialty Chemicals Corporation Cyclic diphenylacetonitriles as stabilizers
EP0612796A1 (en) * 1993-02-23 1994-08-31 Ciba-Geigy Ag Stabilisation of organic pigments
WO1995011464A2 (en) * 1993-10-20 1995-04-27 Minnesota Mining And Manufacturing Company Ultra-flexible retroreflective cube corner composite sheetings and methods of manufacture
US5450235A (en) * 1993-10-20 1995-09-12 Minnesota Mining And Manufacturing Company Flexible cube-corner retroreflective sheeting
WO1996017012A1 (en) * 1994-11-28 1996-06-06 Minnesota Mining And Manufacturing Company Articles exhibiting durable colour and/or fluorescent properties
US5605761A (en) * 1994-11-28 1997-02-25 Minnesota Mining And Manufacturing Company Articles exhibiting durable color containing a polycarbonate, a fluorescent dye and an amine light stabilizer
WO1997008756A1 (en) * 1995-08-28 1997-03-06 Minnesota Mining And Manufacturing Company Durable fluorescent solar collectors
WO1997037252A1 (en) * 1996-04-01 1997-10-09 Reflexite Corporation A color-fast retroreflective structure

Non-Patent Citations (18)

* Cited by examiner, † Cited by third party
Title
Article: Can Zhang et al., "Hindered Amine Light Stabilizers: Effects of Acid Exposure*," Journal of Polymer Science: Part C: Polymer Letters, vol. 24, 1986, pp. 453-456.
Article: Can Zhang et al., Hindered Amine Light Stabilizers: Effects of Acid Exposure*, Journal of Polymer Science: Part C: Polymer Letters , vol. 24, 1986, pp. 453 456. *
Article: J. Guillermo Martinez et al., "Prediction of Photoageing Stability of Plasticised PVC Films Containing UV-Stabilisers," Polymer Degradation and Stability, 54, 1996, pp. 49-55.
Article: J. Guillermo Martinez et al., Prediction of Photoageing Stability of Plasticised PVC Films Containing UV Stabilisers, Polymer Degradation and Stability , 54, 1996, pp. 49 55. *
Article: Marcie McMurrer, "Update: UV Stabilizers," Plastics Compounding, Jan./Feb., 1985, pp. 40-57.
Article: Marcie McMurrer, Update: UV Stabilizers, Plastics Compounding , Jan./Feb., 1985, pp. 40 57. *
Chapter: T. Hjertberg et al., "Thermal Degradation of PVC," Degradation and Stabilisation of PVC, Elsevier Applied Science Publishers, undated pp. 21-79.
Chapter: T. Hjertberg et al., Thermal Degradation of PVC, Degradation and Stabilisation of PVC , Elsevier Applied Science Publishers, undated pp. 21 79. *
Database WPI, Section Ch, Week 8550, Derwent Publications Ltd., London, GB; Class A14, AN 85 315090; XP002069959; Ananymous: PVC With Improved Retention of Heat Stability After Weathering Obtd. by Incorporating a Hindered Amine Light Stabiliser, see abstract & Research Disclosure, vol. 259, No. 001, Emsworth, GB. *
Database WPI, Section Ch, Week 8550, Derwent Publications Ltd., London, GB; Class A14, AN 85-315090; XP002069959; Ananymous: "PVC With Improved Retention of Heat Stability After Weathering--Obtd. by Incorporating a Hindered Amine Light Stabiliser," see abstract & Research Disclosure, vol. 259, No. 001, Emsworth, GB.
Hjertberg, T., & S o rvik, E.M. Thermal Degradation of PVC in Degradation and Stabilisation of PVC (1984) p. 21, 69. *
Hjertberg, T., & Sorvik, E.M. Thermal Degradation of PVC in Degradation and Stabilisation of PVC (1984) p. 21, 69.
Martinez et al., Prediction of Photoageing Stability of Plasticized PVC Films Containing UV Stabilizers , vol. 54, Polymer Degradation and Stability (1996), p. 49. *
Martinez et al., Prediction of Photoageing Stability of Plasticized PVC Films Containing UV-Stabilizers, vol. 54, Polymer Degradation and Stability (1996), p. 49.
McMurrer, Marcie, Update: UV Stabilizers , Plastics Compounding (Jan./Feb. 1985), p. 40 47. *
McMurrer, Marcie, Update: UV Stabilizers, Plastics Compounding (Jan./Feb. 1985), p. 40-47.
Zhang, Can et al., Hindered Amine Light Stabilizers: Effects of Acid Exposure , vol. 24, Journal of Polymer Science: Part C: Polymer Letters (1986) p. 453. *
Zhang, Can et al., Hindered Amine Light Stabilizers: Effects of Acid Exposure, vol. 24, Journal of Polymer Science: Part C: Polymer Letters (1986) p. 453.

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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US6526588B2 (en) * 1997-10-23 2003-03-04 3M Innovative Properties Company Stabilization of fluorescent dyes in vinyl chloride articles using hindered amine light stabilizers
US20060292347A1 (en) * 1997-10-23 2006-12-28 3M Innovative Properties Company Stabilization of fluorescent dyes in vinyl articles using hindered amine light stabilizers
US7449514B2 (en) 1997-10-23 2008-11-11 3M Innovative Properties Company Stabilization of fluorescent dyes in vinyl articles using hindered amine light stabilizers
US6406798B2 (en) * 1997-10-23 2002-06-18 3M Innovative Properties Company Stabilization of fluorescent dyes in vinyl articles using hindered amine light stabilizers
US20050213213A1 (en) * 1997-10-23 2005-09-29 3M Innovative Properties Company Stabilization of fluorescent dyes in vinyl articles using hindered amine light stabilizers
US6323266B2 (en) 1998-01-21 2001-11-27 Reflexite Corporation Extended life fluorescence polyvinyl chloride sheeting
US6552106B2 (en) 1998-01-21 2003-04-22 Reflexite Corporation Extended life fluorescence polyvinyl chloride sheeting
US6734235B2 (en) 1998-01-21 2004-05-11 Reflexite Corporation Extended life fluorescence polyvinyl chloride sheeting
US6511256B1 (en) 1999-05-27 2003-01-28 Avery Dennison Corporation Pavement marker with improved daytime visibility and fluorescent durability
US6533961B2 (en) * 2000-02-22 2003-03-18 3M Innovative Properties Company Durable fluorescent organic pigments and methods of making
US20030102460A1 (en) * 2000-02-22 2003-06-05 3M Innovative Properties Company Durable fluorescent organic pigments and methods of making
US20020041136A1 (en) * 2000-06-28 2002-04-11 Kenichi Nishikawa Spark plug
US6831396B2 (en) * 2000-06-28 2004-12-14 Ngk Spark Plug Co., Ltd. Spark plug with glaze and marking
US6537679B1 (en) 2000-11-09 2003-03-25 Avery Dennison Corporation Fluorescent articles of glycol-modified polyethylene terephthalate
US6972147B1 (en) 2000-11-09 2005-12-06 Avery Dennison Corporation Fluorescent polymeric articles fabricated from U.V. light absorbing polymer
US6514594B1 (en) 2000-11-09 2003-02-04 Avery Dennison Corporation Fluorescent polymeric articles having screening layer formed from U.V. light absorbing polymer
US6531205B1 (en) 2001-02-14 2003-03-11 Avery Dennison Corporation Fluorescent yellow retroreflective sheeting
US6689391B2 (en) 2001-03-30 2004-02-10 Council Of Scientific & Industrial Research Natural non-polar fluorescent dye from a non-bioluminescent marine invertebrate, compositions containing the said dye and its uses
US6916492B2 (en) 2001-03-30 2005-07-12 Council Of Scientific & Industrial Research Natural nontoxic multicolor fluorescent protein dye from a marine invertebrate, compositions containing the said dye and its uses
US6582730B2 (en) 2001-03-30 2003-06-24 Council Of Scientific & Industrial Research Natural fluorescent dye obtained from a marine invertebrate, compositions containing the said dye and their uses
WO2003016391A3 (en) * 2001-08-20 2003-12-04 3M Innovative Properties Co Articles containing thioxanthone dyes
US6713636B2 (en) 2001-08-20 2004-03-30 3M Innovative Properties Company Thloxanthone dyes with improved solubility and a method of preparing 2-oxybenzanthrones as intermediate materials for making of these dyes
US6841236B2 (en) 2001-08-20 2005-01-11 3M Innovative Properties Co. Articles containing thioxanthone dyes
US20030061671A1 (en) * 2001-08-20 2003-04-03 Shershukov Viktor Mihailovich Thioxanthone dyes with improved solubility and a method of preparing 2-oxybenzanthrones as intermediate materials for making of these dyes
WO2003016391A2 (en) * 2001-08-20 2003-02-27 3M Innovative Properties Company Articles containing thioxanthone dyes
US20050080273A1 (en) * 2001-09-05 2005-04-14 Usha Goswami Multiple fluorescent natural dye compound from a marine organism and method of use thereof
US6956122B2 (en) 2001-09-05 2005-10-18 Council Of Scientific & Industrial Research Multiple fluorescent natural dye compound from a marine organism
US20030096988A1 (en) * 2001-09-05 2003-05-22 Usha Goswami Multiple fluorescent natural dye compound from a marine organism
US20050137393A1 (en) * 2001-09-05 2005-06-23 Usha Goswami Multiple fluorescent natural dye compound from a marine organism
US7012093B2 (en) 2001-09-05 2006-03-14 Council Of Scientific & Industrial Research Multiple fluorescent natural dye compound from a marine organism and method of use thereof
US6683124B2 (en) 2001-09-27 2004-01-27 Clariant Finance (Bvi) Limited Fluorescent pigment compositions
EP2620280A1 (en) 2002-04-30 2013-07-31 Avery Dennison Corporation Fluorescent articles having multiple film layers
US7618710B2 (en) 2002-04-30 2009-11-17 Avery Dennison Corporation Fluorescent articles having multiple film layers
US8034436B2 (en) 2002-04-30 2011-10-11 Avery Dennison Corporation Fluorescent article having multiple layers
US20030203212A1 (en) * 2002-04-30 2003-10-30 Guang-Xue Wei Fluorescent articles having multiple film layers
US7618709B2 (en) 2002-04-30 2009-11-17 Avery Dennison Corporation Fluorescent articles having multiple film layers
US20070184278A1 (en) * 2002-04-30 2007-08-09 Guang-Xue Wei Fluorescent articles having multiple film layers
US7264880B2 (en) 2002-04-30 2007-09-04 Avery Dennison Corporation Fluorescent articles having multiple film layers
US20080182110A1 (en) * 2002-04-30 2008-07-31 Avery Dennison Corporation Fluorescent article having multiple layers
US20030203211A1 (en) * 2002-04-30 2003-10-30 Guang-Xue Wei Fluorescent articles having multiple film layers
WO2004073042A2 (en) * 2003-02-12 2004-08-26 Insite Solutions, Llc Article with fabric-backed decorative element and method of fabricating the same
WO2004073042A3 (en) * 2003-02-12 2004-11-11 Insite Solutions Llc Article with fabric-backed decorative element and method of fabricating the same
US7396579B2 (en) 2003-05-15 2008-07-08 3M Innovative Properties Company Fluorescent red-orange retroreflective sheeting
US20040227997A1 (en) * 2003-05-15 2004-11-18 3M Innovative Properties Company Fluorescent red-orange retroreflective sheeting
EP1481799A1 (en) * 2003-05-29 2004-12-01 Alcan International Limited Optical brighteners for display panels
US20050154098A1 (en) * 2004-01-09 2005-07-14 Reflexite Corporation Fade-resistant fluorescent retroreflective articles
WO2005071010A1 (en) * 2004-01-09 2005-08-04 Reflexite Corporation Fade-resistant fluorescent retroreflective articles
US20070008790A1 (en) * 2004-05-26 2007-01-11 Buechler Troy R Optical brighteners for display panels
US20150247297A1 (en) * 2012-11-28 2015-09-03 Evonik Industries Ag New type of road markings for supporting the environment detection of vehicles
US9701846B2 (en) * 2012-11-28 2017-07-11 Evonik Roehm Gmbh Type of road markings for supporting the environment detection of vehicles
US10800970B2 (en) 2015-07-17 2020-10-13 Toray Industries, Inc. Color conversion composition, color conversion film and backlight unit, display and lighting device each comprising same
US20200325397A1 (en) * 2020-06-25 2020-10-15 Battle Sight Technologies, LLC Article of manufacture using an industrial or commercial manufacturing process, wherein the article of manufacture comprises an infrared (ir) phosphorescent material
US11473012B2 (en) * 2020-06-25 2022-10-18 Battle Sight Technologies, LLC Article of manufacture using an industrial or commercial manufacturing process, wherein the article of manufacture comprises an infrared (IR) phosphorescent material
CN112430393A (en) * 2020-11-20 2021-03-02 广州辰东新材料有限公司 Ultraviolet-resistant thermoplastic polyamide composite material for laser welding and preparation method thereof
CN114316471A (en) * 2021-12-31 2022-04-12 天津利安隆新材料股份有限公司 Composite light stabilizer suitable for rigid polyvinyl chloride material, rigid polyvinyl chloride material and preparation method thereof

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